CN109964350A - The manufacturing method of electrochemical reaction unit, electrochemical reaction battery pack and electrochemical reaction unit - Google Patents
The manufacturing method of electrochemical reaction unit, electrochemical reaction battery pack and electrochemical reaction unit Download PDFInfo
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- CN109964350A CN109964350A CN201780071821.6A CN201780071821A CN109964350A CN 109964350 A CN109964350 A CN 109964350A CN 201780071821 A CN201780071821 A CN 201780071821A CN 109964350 A CN109964350 A CN 109964350A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
- H01M8/2432—Grouping of unit cells of planar configuration
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/248—Means for compression of the fuel cell stacks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Leakproofness of the stress of the thermal expansion difference due to two components caused by glass capsulation portion generates between two components is inhibited to reduce.A kind of electrochemical reaction unit, has: single battery comprising electrolyte layer and the air pole and fuel electrodes relative to each other along the 1st direction across electrolyte layer；And one or more member of formation, wherein, the electrochemical reaction unit has glass capsulation portion, the glass capsulation portion with it is in single battery and one or more member of formation, contact along two relative to each other components of the 1st direction, containing glass, multiple crystal grain that the ratio very little relative to the crossfoot as the size on the 2nd direction orthogonal with the 1st direction as the linear foot cun of the size on the 1st direction is 1.5 or more are contained in glass capsulation portion.
Description
Technical field
Technology disclosed in this specification is related to a kind of electrochemical reaction unit.
Background technique
As one of the type of fuel cell to be generated electricity using the electrochemical reaction between hydrogen and oxygen, there is known solid
The fuel cell (hereinafter referred to as " SOFC ") of oxide body shape.The fuel cell power generation unit for constituting SOFC has: fuel cell
Monomer comprising electrolyte layer and the air pole and fuel electrodes relative to each other along the 1st direction across electrolyte layer；It is a pair of mutual
Connected device, it is relative to each other along the 1st direction across fuel cell；Separator is formed with through hole, surrounds the through hole
The peripheral part of part and fuel cell engage (for example, Nian Jie), division forming face is to the air chamber of air pole and faces
The fuel chambers of fuel electrodes.
In addition, there are following situations in fuel cell power generation unit: in two structures relative to each other along the 1st direction
The glass capsulation for making crystallization of glass material at the space configuration between component (for example, above-mentioned separator and connectors) and being formed
Portion, so that two member of formation electrical isolations, while ensuring gas tightness (see, for example patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-183376 bulletin
Summary of the invention
Problems to be solved by the invention
Two member of formation contacted with glass capsulation portion are thermally expanded since the power generation of fuel cell power generation unit acts.
At this point, due to two member of formation thermal expansion difference and stretched by each member of formation along 2nd direction orthogonal with the 1st direction
A member of formation side of the amount in glass capsulation portion part and another member of formation side part it is sometimes different, with this
Together, there are the following problems: generating along the crackle in the 2nd direction in glass capsulation portion, as a result, the leakproofness between member of formation
It reduces.
It in addition, such problems is not only in plate shaped SOFC, but also is also common problem in the SOFC of such as tubular.
In addition, such problems constitute carry out using the cell reaction of water the soild oxide shape of the generation of hydrogen electrolytic cell (with
Electrolytic cell unit down referred to as " SOEC ") is also common problem.In addition, in the present specification, by fuel cell and electricity
Xie Chi is referred to as electrochemical reaction single battery, and fuel cell power generation unit and electrolytic cell unit are referred to as electrochemical reaction list
Position.
In the present specification, the open at least part of technology that can be solved the problem above-mentioned.
The solution to the problem
Technology disclosed in this specification can be realized as form below.
(1) electrochemical reaction unit disclosed in this specification has: single battery comprising electrolyte layer and across
The electrolyte layer air pole and fuel electrodes relative to each other along the 1st direction；With one or more member of formation, in the electrification
It learns in reacton, has glass capsulation portion, the glass capsulation portion and the single battery and one or more described member of formation
In, contact along two relative to each other components of the 1st direction, which contains glass, the glass capsulation
Multiple crystal grain that the linear foot cun ratio very little relative to crossfoot is 1.5 or more are contained in portion, and the linear foot cun is as on the 1st direction
Size, the crossfoot cun is as the size on the 2nd direction orthogonal with the 1st direction.According to this electrochemical reaction unit, glass
Sealing contains multiple crystal grain (hereinafter referred to as " lengthwise crystal grain ") that the linear foot cun ratio very little relative to crossfoot is 1.5 or more.By
This, even if being generated due to the stress of the thermal expansion difference of two components as sealed object in glass capsulation portion, in lengthwise crystalline substance
Under the action of grain, the transverse crack than extending along the 2nd direction (transverse direction) is also easy to along the longitudinal crack that the 1st direction (longitudinal direction) extends
It is preferentially generated in glass capsulation portion, therefore, stress release can be made using longitudinal crack.That is, by crackle preferentially along two structures
The 1st opposite direction of part is formed, and so as to inhibit crackle to be formed along the 2nd direction, gas is inhibited to wear between the two components
It crosses.Thus, it is possible to which the leakproofness between two components as sealed object is inhibited to reduce.
(2) in above-mentioned electrochemical reaction unit, described two components are the single battery and at least part in institute
State the member of formation opposite with the single battery on the 1st direction.According to this electrochemical reaction unit, it is able to suppress monomer
Leakproofness between battery and member of formation reduces.
(3) in above-mentioned electrochemical reaction unit, the member of formation opposite with the single battery is separator, should
Separator is formed with through hole, and the part for surrounding the through hole is engaged with the peripheral part of the single battery, which draws
Separate the fuel chambers in face of the air chamber of the air pole and in face of the fuel electrodes.It, can according to this electrochemical reaction unit
The leakproofness between single battery and separator is inhibited to reduce.
(4) in above-mentioned electrochemical reaction unit, described two components be along the 1st direction it is relative to each other the 1st
Member of formation and the 2nd member of formation.According to this electrochemical reaction unit, lengthwise crystal grain is contained in glass capsulation portion.Even if rising as a result,
Because the stress of the thermal expansion difference between the 1st member of formation and the 2nd member of formation generates in glass capsulation portion, in lengthwise crystal grain
Under effect, it is also easy to along the longitudinal crack that the 1st direction (longitudinal direction) extends more preferential than the transverse crack extended along the 2nd direction (transverse direction)
It is generated in glass capsulation portion, therefore, stress release can be made using longitudinal crack.That is, by crackle along the 1st member of formation and the
The 1st opposite orientation preferentially of 2 member of formation is formed, and so as to inhibit crackle to be formed along the 2nd direction, inhibits gas the 1st
It is passed through between member of formation and the 2nd member of formation.Thus, it is possible to inhibit the sealing between the 1st member of formation and the 2nd member of formation
Property reduce.
(5) in above-mentioned electrochemical reaction unit, one of the 1st member of formation and the 2nd member of formation are
Connectors.Thereby, it is possible to inhibit the leakproofness between connectors and the member of formation opposite with the connectors to reduce.
(6) in above-mentioned electrochemical reaction unit, it also can be set to the linear foot cun of at least one of the multiple crystal grain
It is 30% or more structure of the thickness in the 1st direction in the glass capsulation portion.It is multiple according to this electrochemical reaction unit
The linear foot cun of at least one of crystal grain is 30% or more of the thickness of the longitudinal direction (the 1st direction) in glass capsulation portion, therefore, longitudinal crack
Be easier to preferentially generate in glass capsulation portion than transverse crack, therefore, can more effectively inhibit single battery and member of formation it
Between or leakproofness between the 1st member of formation and the 2nd member of formation reduce.
(7) in above-mentioned electrochemical reaction unit, it also can be set to the linear foot cun of at least one of the multiple crystal grain
It is 50% or more structure of the thickness in the 1st direction in the glass capsulation portion.It is multiple according to this electrochemical reaction unit
The linear foot cun of at least one of crystal grain is 50% or more of the thickness of the longitudinal direction (the 1st direction) in glass capsulation portion, therefore, even if producing
Transverse crack is given birth to, the progress of the transverse crack is also easy to be inhibited by crystal grain, and as a result, it is possible to more effectively inhibit single battery and structure
It is reduced at the leakproofness between component or between the 1st member of formation and the 2nd member of formation.
(8) in electrochemical reaction battery pack disclosed in this specification, at least the 1 of multiple electrochemical reaction units
A is electrochemical reaction unit documented by any one of above-mentioned (1)~(7).
(9) manufacturing method of electrochemical reaction unit disclosed in this specification is the manufacture of following electrochemical reaction unit
Method, the electrochemical reaction unit have: single battery comprising electrolyte layer and across the electrolyte layer along the 1st
Direction air pole and fuel electrodes relative to each other；One or more member of formation and glass capsulation portion, the glass capsulation portion with
It is in the single battery and one or more described member of formation, connect along two relative to each other components of the 1st direction
Glass is contained in touching, the glass capsulation portion, and it is 1.5 or more that linear foot cun is contained relative to the ratio of crossfoot cun in the glass capsulation portion
Multiple crystal grain, the linear foot cun is as the size on the 1st direction, and the crossfoot cun is as 2nd side orthogonal with the 1st direction
Upward size comprises the following steps in the manufacturing method of the electrochemical reaction unit: preparing the single battery and described
The process of one or more member of formation；Configuration contains Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce between described two components
In at least one kind of element kind layer and glass process；And in described kind of layer and the configurations of glass to described two components
Between in the state of, make the glass melting, later, make melting after the glass crystallization, so that it is close to form the glass
The process in envelope portion.According to the manufacturing method of this electrochemical reaction unit, between the two components configuration containing Ba, Ca, Mg, Al,
The kind layer and glass of at least one kind of element in La, Ti, Cr, Zr, Ce, make glass melting, crystallization, so as to formed containing
The glass capsulation portion of lengthwise crystal grain.
(10) in the manufacturing method of above-mentioned electrochemical reaction unit, described two components are the single batteries and at least
A part member of formation opposite with the single battery on the 1st direction.According to the manufacture of this electrochemical reaction unit
Method, configuration contains at least one kind of member in Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce between single battery and member of formation
The kind layer and glass of element make glass melting, crystallization, so as to form the glass capsulation portion containing lengthwise crystal grain.
(11) in the manufacturing method of above-mentioned electrochemical reaction unit, described two components be along the 1st direction that
This opposite the 1st member of formation and the 2nd member of formation.According to the manufacturing method of this electrochemical reaction unit, in the 1st member of formation
Kind layer and glass containing at least one kind of element in Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce are configured between the 2nd member of formation
Glass makes glass melting, crystallization, so as to form the glass capsulation portion containing lengthwise crystal grain.
In addition, technology disclosed in this specification can be realized with various forms, it can be with such as electrochemical reaction unit (fuel
Cell power generation unit or electrolytic cell unit), have the electrochemical reaction battery pack (fuel cell units of multiple electrochemical reaction units
Or electrolytic cell), their forms such as manufacturing method realize.
Detailed description of the invention
Fig. 1 is the perspective view for indicating the surface structure of fuel cell unit 100 of present embodiment.
Fig. 2 is the explanatory diagram for indicating the XZ cross section structure of the fuel cell unit 100 at the position of the II-II of Fig. 1.
Fig. 3 is the explanatory diagram for indicating the YZ cross section structure of the fuel cell unit 100 at the position of the III-III of Fig. 1.
Fig. 4 is to indicate that the XZ of two power generation units 102 adjacent to each other at position identical with section shown in Fig. 2 is cut
The explanatory diagram of face structure.
Fig. 5 is to indicate that the YZ of two power generation units 102 adjacent to each other at position identical with section shown in Fig. 3 is cut
The explanatory diagram of face structure.
Fig. 6 is the explanatory diagram for indicating the structure of the 1st glass sealing material 52 of present embodiment.
Fig. 7 is the flow chart for indicating the manufacturing method of fuel cell unit 100.
Specific embodiment
A. embodiment:
A-1. structure:
(structure of fuel cell unit 100)
Fig. 1 is the perspective view for indicating the surface structure of the fuel cell unit 100 in present embodiment, and Fig. 2 indicates Fig. 1
The explanatory diagram of the XZ cross section structure of fuel cell unit 100 at the position of II-II, Fig. 3 are the positions for indicating the III-III of Fig. 1
The explanatory diagram of the YZ cross section structure of the fuel cell unit 100 at place.In the various figures shown with for determining the mutually orthogonal of direction
XYZ axis.In the present specification, for conveniently, Z axis positive direction is known as upper direction, Z axis negative direction is known as lower direction, but combustion
Expect that battery pack 100 actually can also be to be arranged from such towards different directions.For also the same after Fig. 4.
Fuel cell unit 100 has multiple (in the present embodiment, 7) power generation unit 102, the 1st end plate 104, the 2nd end
Plate 106 and collector plate 18.7 power generation units 102 are along scheduled orientation (in the present embodiment, up and down direction (Z
Axis direction)) it is arranged.Collector plate 18 is configured at the downside of the power generation unit 102 under being located at most.1st end plate 104 is configured at position
The upside of power generation unit 102 on most, the 2nd end plate 106 are configured at the downside of collector plate 18.In addition, above-mentioned orientation (on
Lower direction) it is equivalent to the 1st direction in claims.
In each layer (power generation unit 102, the 1st end plate 104 and the 2nd end plate 106, collector plate for constituting fuel cell unit 100
18) the peripheral part around Z-direction is formed with multiple (in the present embodiment, the 8) holes penetrated through along up and down direction, in each layer
It is formed and mutual corresponding hole is connected to one another along up and down direction, constituted from the 1st end plate 104 to the 2nd end plate 106 along upper and lower
The through hole 108 that direction extends.In the following description, existing will be in order to constitute through hole 108 and in fuel cell unit 100
The case where hole that each layer is formed is also referred to as through hole 108.
In each through hole 108 inserted with the bolt 22 extended along up and down direction, fuel cell unit 100 is by bolt 22 and embedding
The nut 24 for closing the two sides of bolt 22 fastens.
The outer diameter of the axle portion of each bolt 22 is smaller than the internal diameter of each through hole 108.Therefore, in the periphery of the axle portion of each bolt 22
Ensure there is space between face and the inner peripheral surface of each through hole 108.As depicted in figs. 1 and 2, by be located at fuel cell unit 100 around Z
1 in the periphery in the direction bolt 22 near the midpoint on (side of the X-axis positive direction side in while two parallel with Y-axis)
The space of (bolt 22A) and the formation of through hole 108 inserted with bolt 22A imports manifold 161 as oxidant gas and plays
Function, oxidant gas OG are imported manifold 161, the oxidant from external oxidant gas that imports of fuel cell unit 100
It is the gas flow path for supplying oxidant gas OG to each power generation unit 102 that gas, which imports manifold 161, by the phase for being located at the side
It the bolt 22 (bolt 22B) near the midpoint on (side of the X-axis negative direction side in while two parallel with Y-axis) tossed about and inserts
The space for entering to have the through hole 108 of bolt 22B to be formed is functioned as oxidant gas discharge manifold 162, oxidant gas
Manifold 162 is discharged in body will be as from the oxidant exhaust OOG of gas that the air chamber 166 of each power generation unit 102 ejects to combustion
Expect the external discharge of battery pack 100.In addition, in the present embodiment, as oxidant gas OG, such as air can be used.
In addition, as shown in figures 1 and 3,1 side in the periphery around Z-direction by being located at fuel cell unit 100 is (with X-axis
Y-axis positive direction side of parallel two in while) midpoint near bolt 22 (bolt 22D) and inserted with bolt 22D
The space that is formed of through hole 108 functioned as fuel gas importing manifold 171, fuel gas FG is by from fuel cell unit
100 external fuel gas that imports imports manifold 171, which imports manifold 171 for fuel gas FG to each hair
Electric unit 102 supplies, by be located at this while opposite side while (Y-axis negative direction side of two parallel with X-axis in while)
It is arranged as fuel gas in the space that bolt 22 (bolt 22E) near midpoint and the through hole 108 inserted with bolt 22E are formed
Manifold 172 functions out, and fuel gas is discharged manifold 172 and will eject as from the fuel chambers 176 of each power generation unit 102
External discharge of the exhaust combustion gases FOG of gas to fuel cell unit 100.In addition, in the present embodiment, as fuel gas
Hydrogen-rich gas made of being modified to such as town gas can be used in FG.
Fuel cell unit 100 is provided with 4 gas passage components 27.Each gas passage component 27 is formed by metal, tool
There is the branch portion 29 of the main part 28 of hollow tube-shape and the hollow tube-shape of the side branches from main part 28.The hole of branch portion 29 with
The hole of main part 28 is connected to.Gas pipe (not shown) is connected in the branch portion 29 of each gas passage component 27.In addition, as schemed
Shown in 2, it is configured to the main part to form the gas passage component 27 of position for the bolt 22A that oxidant gas imports manifold 161
28 hole imports manifold 161 with oxidant gas and is connected to, and is configured to the bolt 22B's to form oxidant gas discharge manifold 162
The hole of the main part 28 of the gas passage component 27 of position is connected to oxidant gas discharge manifold 162.In addition, as shown in figure 3,
Be configured to be formed fuel gas import manifold 171 bolt 22D position gas passage component 27 main part 28 hole with
Fuel gas imports manifold 171 and is connected to, be configured to be formed the position of bolt 22E of fuel gas discharge manifold 172 gas it is logical
The hole of the main part 28 of road component 27 is connected to fuel gas discharge manifold 172.
As shown in Figures 2 and 3, crystallization of glass material and the 1st glass sealing material 52 that is formed are between being fitted to bolt
The nut 24 of 22 side (upside) and constitute fuel cell unit 100 upper end the 1st end plate 104 uper side surface between, with
And it is fitted under the nut 24 of the other side (downside) of bolt 22 and the 2nd end plate 106 of the lower end of composition fuel cell unit 100
Between side surface.But, in the position for being provided with gas passage component 27, gas passage component 27 and gas is respectively configured
1st glass sealing material 52 of the upper side and lower side of passage member 27 is between nut 24 and the surface of the 2nd end plate 106.?
What the hole that the 1st glass sealing material 52 is formed with the main part 28 with above-mentioned each through hole 108, gas passage component 27 was connected to
Hole.Across the 1st glass sealing material 52 along orientation two electroconductive members adjacent to each other (for example, 24 He of nut
1st end plate 104) it is electrically insulated by the 1st glass sealing material 52, and the gas tightness between two electroconductive members is ensured that.This
Outside, above-mentioned 24 and the 1st end plate 104 of nut is equivalent to the 1st member of formation and the 2nd member of formation in claims.In addition, the
1 glass sealing material 52 is equivalent to the glass capsulation portion in claims.
(structure of end plate 104,106)
1st end plate 104 and the 2nd end plate 106 are the electroconductive members of substantially rectangular writing board shape, by such as stainless steel shape
At.1st end plate 104 has along direction (such as X-axis negative direction) outstanding 1st protruding portion substantially orthogonal with orientation
14.1st protruding portion 14 of the 1st end plate 104 is functioned as the output terminal of the side of the positive electrode of fuel cell unit 100.
(structure of collector plate 18)
Collector plate 18 is the electroconductive member of substantially rectangular writing board shape, is formed by such as stainless steel.Collector plate 18 has
For along direction (such as X-axis positive direction) outstanding 2nd protruding portion 16 substantially orthogonal with orientation.The protrusion of collector plate 18
Portion 16 is functioned as the output terminal of the negative side of fuel cell unit 100.
Crystallization of glass material and the insulating materials 57 such as the 2nd glass sealing material 54 formed and mica are between collector plate 18
Between the 2nd end plate 106.On insulating materials 57, it is formed with hole in position corresponding with above-mentioned each through hole 108, at this
The inside in hole is configured with the 2nd glass sealing material 54.It is formed with and above-mentioned each through hole 108 in the 2nd glass sealing material 54
The hole of connection.As across the 2nd glass sealing material 54 and along the collection of orientation two electroconductive members adjacent to each other
Battery plate 18 and the 2nd end plate 106 are electrically insulated by the 2nd glass sealing material 54, and the gas between collector plate 18 and the 2nd end plate 106
Leakproofness is ensured that.
(structure of power generation unit 102)
Fig. 4 is to indicate that the XZ of two power generation units 102 adjacent to each other at position identical with section shown in Fig. 2 is cut
The explanatory diagram of face structure, Fig. 5 are the two power generation units adjacent to each other indicated at position identical with section shown in Fig. 3
The explanatory diagram of 102 YZ cross section structure.
As shown in Figure 4 and Figure 5, have single battery 110, separator as the power generation unit 102 of the minimum unit of power generation
120, air pole side frame 130, air pole side collector 134, fuel electrodes side frame 140, fuel electrodes side collector 144 and
The top layer of composition power generation unit 102 and undermost a pair of of connectors 150.In separator 120, air pole side frame 130, combustion
Expect pole side frame 140, the peripheral part around Z-direction of connectors 150 is formed with and the through hole 108 for the above-mentioned insertion of bolt 22
Corresponding hole.In addition, power generation unit 102 is equivalent to the electrochemical reaction unit in claims.In addition, separator 120
The member of formation being equivalent in claims.Moreover, one in a pair of of connectors 150 is equivalent to right with separator 120
The 1st member of formation and the 2nd member of formation in claim.
Connectors 150 are the electroconductive members of substantially rectangular writing board shape, are formed by such as ferrite-group stainless steel.Mutually
Connected device 150 ensures the conducting of the electricity between power generation unit 102, and prevents mixing of the reaction gas between the unit 102 that generates electricity.This
Outside, in the present embodiment, in the case where two power generation units 102 are adjacent to configuration, 1 connectors 150 is by adjacent two
A power generation unit 102 is shared.That is, the connectors 150 of the upside in certain power generation unit 102 are the same as the upside with the power generation unit 102
The connectors 150 of downside in adjacent another power generation unit 102 are identical components.Therefore, certain connectors 150 is in face of certain hair
The air chamber 166 in face of aftermentioned air pole 114 in electric unit 102, and in face of adjacent with the upside of the power generation unit 102
The fuel chambers 176 in face of aftermentioned fuel electrodes 116 in another power generation unit 102.In addition, fuel cell unit 100 has the 1st end
Plate 104 and collector plate 18, therefore, in fuel cell unit 100, the power generation unit 102 on most does not have the interconnection of upside
Device 150, the power generation unit 102 under most do not have the connectors 150 of downside (referring to Fig. 2 and Fig. 3).
Single battery 110 has electrolyte layer 112 and across electrolyte layer 112 along up and down direction (power generation unit 102
The orientation of arrangement) air pole 114 and fuel electrodes 116 relative to each other.In addition, the single battery 110 of present embodiment is
Utilize the single battery of the fuel electrodes of 116 support electrolyte matter layer 112 of fuel electrodes and air pole 114 bearing shape.
Electrolyte layer 112 is substantially rectangular writing board shape component, contains at least Zr, by such as YSZ (yttria-stabilized
Zirconium oxide), ScSZ (scandia stabilized zirconium oxide), the soild oxides such as CaSZ (stable calcium oxide zirconium oxide) are formed.It is empty
Air exhaustion 114 is substantially rectangular writing board shape component, by such as perofskite type oxide (such as LSCF (lanthanum-strontium ferro-cobalt aoxidize
Object), LSM (lanthanum-strontium-manganese oxide), LNF (lanthanum ferronickel)) formed.Fuel electrodes 116 are substantially rectangular writing board shape components, by example
Such as Ni (nickel), cermet, the formation of Ni based alloy, cermet are formed by Ni and ceramic particle.In this way, present embodiment
Single battery 110 (power generation unit 102) is to use soild oxide as the soild oxide shape fuel cell of electrolyte
(SOFC)。
Separator 120 is to be formed about the frame-like in the substantially rectangular hole 121 along up and down direction perforation in center
Component, formed by such as metal.The peripheral part in the hole 121 in separator 120 and the air pole 114 in electrolyte layer 112
Side surface peripheral part it is opposite.Separator 120 utilizes solder (such as Ag solder) shape by being configured to its opposite part
At joint portion 124 engaged with electrolyte layer 112 (single battery 110).In face of the air chamber 166 of air pole 114 and in face of combustion
The fuel chambers 176 of material pole 116 are demarcated by separator 120, in the peripheral part of single battery 110 from an electrode side to another
The leakage of the gas of a electrode side is suppressed.In addition, the single battery 110 for being bonded to separator 120 is also referred to as band separator
Single battery.
Air pole side frame 130 is to be formed about the substantially rectangular hole 131 penetrated through along up and down direction in center
The component of frame-like is formed by insulators such as such as micas.The hole 131 of air pole side frame 130 is constituted in face of air pole 114
Air chamber 166.Surface of the air pole side frame 130 with the opposite side of the side opposite with electrolyte layer 112 in separator 120
Peripheral part and the peripheral part on surface of the side opposite with air pole 114 in connectors 150 contact.That is, air pole side
Frame 130 is configured at along between the adjacent separator 120 of orientation and connectors 150.In addition, power generation unit 102 is wrapped
It is electrically insulated between a pair of of the connectors 150 contained by air pole side frame 130.In addition, being formed in air pole side frame 130: oxidation
Agent gas supplies intercommunicating pore 132, and oxidant gas is imported manifold 161 and is connected to air chamber 166；It is discharged with oxidant gas
Air chamber 166 is connected to by intercommunicating pore 133 with oxidant gas discharge manifold 162.
In the 3rd glass that the inside of each through hole 108 of air pole side frame 130 is formed configured with crystallization of glass material
Glass sealing material 56.That is, across air pole side frame 130 and between adjacent separator 120 and connectors 150, to surround
The mode of each manifold is configured with the 3rd glass sealing material 56.As across the 3rd glass sealing material 56 and along orientation that
The separator 120 and connectors 150 of this two adjacent electroconductive member are electrically insulated by the 3rd glass sealing material 56, and separate
Gas tightness between part 120 and connectors 150 is ensured that.In addition, the 3rd glass sealing material 56 is equivalent to claims
In glass capsulation portion.
Fuel electrodes side frame 140 is to be formed about the substantially rectangular hole 141 penetrated through along up and down direction in center
The component of frame-like is formed by such as metal.The hole 141 of fuel electrodes side frame 140 constitutes the fuel chambers for facing fuel electrodes 116
176.Fuel electrodes side frame 140 with the surface of the side opposite with electrolyte layer 112 in separator 120 peripheral part and mutually
The peripheral part on the surface of the side opposite with fuel electrodes 116 in connected device 150 contacts.In addition, in the formation of fuel electrodes side frame 140
Have: fuel gas supplies intercommunicating pore 142, and fuel gas is imported manifold 171 and is connected to fuel chambers 176；It is arranged with fuel gas
Fuel chambers 176 are connected to by intercommunicating pore 143 out with fuel gas discharge manifold 172.
Fuel electrodes side collector 144 is configured in fuel chambers 176.Fuel electrodes side collector 144 has connectors counterpart
146, electrode counterpart 145 and the interconnecting piece 147 that electrode counterpart 145 is connected with connectors counterpart 146, by for example
The formation such as nickel, nickel alloy, stainless steel.Electrode counterpart 145 is the same as the side opposite with electrolyte layer 112 in fuel electrodes 116
The surface of opposite side contacts, and connectors counterpart 146 connects with the surface of the side opposite with fuel electrodes 116 in connectors 150
Touching.But, as described so, in fuel cell unit 100, the power generation unit 102 under most does not have the connectors of downside
150, therefore, the connectors counterpart 146 in the power generation unit 102 is contacted with the surface of collector plate 18.Fuel electrodes side collector
144 be such structure, and therefore, fuel electrodes 116 and connectors 150 (or collector plate 18) are electrically connected.In addition, opposite in electrode
Configured with the spacer 149 formed by such as mica between portion 145 and connectors counterpart 146.Therefore, fuel electrodes side collector
144 follow the deformation that caused power generation unit 102 is changed by temperature cycle, reaction gas pressure, fuel electrodes 116 and connectors
The electrical connection by means of fuel electrodes side collector 144 between 150 is well maintained.
Air pole side collector 134 is configured in air chamber 166.Air pole side collector 134 is by multiple substantially quadrangulars
The collector element 135 of shape is constituted, and is formed by such as ferrite-group stainless steel.Air pole side collector 134 is the same as in air pole 114
The side opposite with electrolyte layer 112 opposite side surface and one opposite with air pole 114 in connectors 150
The surface of side contacts.But, as described so, in fuel cell unit 100, on the power generation unit 102 on most does not have
The connectors 150 of side, therefore, the air pole side collector 134 of the power generation unit 102 are contacted with the surface of the 1st end plate 104.Such as
This, air pole 114 and connectors 150 (or the 1st end plate 104) are electrically connected by air pole side collector 134.In addition, air pole side
The component that collector 134 and connectors 150 can also be formed as one.In addition, fuel cell unit 100 is equivalent to claims
In electrochemical reaction battery pack.In addition, constituting single battery 110, the separator 120, air pole side frame of power generation unit 102
130, air pole side collector 134, fuel electrodes side frame 140, fuel electrodes side collector 144, a pair of of connectors 150, end plate
104,106, collector plate 18, nut 24, gas passage component 27 are equivalent to the multiple composition structures for constituting electrochemical reaction battery pack
Part.
A-2. the movement of fuel cell unit 100:
As shown in Figure 2 and Figure 4, if oxidant gas OG is via the position for importing manifold 161 with setting to oxidant gas
The gas pipe (not shown) that connects of branch portion 29 of gas passage component 27 be supplied to, then oxidant gas OG via
The branch portion 29 of gas passage component 27 and the hole of main part 28 are imported manifold 161 to oxidant gas and are supplied, from oxidant
Gas imports manifold 161 and is supplied via the oxidant gas supply intercommunicating pore 132 of each power generation unit 102 to air chamber 166.Separately
Outside, as shown in Figure 3 and Figure 5, if fuel gas FG is via the gas passage with setting to the position of fuel gas importing manifold 171
The gas pipe (not shown) that the branch portion 29 of component 27 connects is supplied to, then fuel gas FG is via gas passage component
27 branch portion 29 and the hole of main part 28 are imported manifold 171 to fuel gas and are supplied, and are imported manifold 171 from fuel gas and are passed through
It is supplied from the fuel gas supply intercommunicating pore 142 of each power generation unit 102 to fuel chambers 176.
If oxidant gas OG by each power generation unit 102 the supply of air chamber 166, fuel gas FG is by fuel chambers
176 supplies, then carry out the power generation of the electrochemical reaction based on oxidant gas OG and fuel gas FG in single battery 110.
The electric power generation reaction is exothermic reaction.In each power generation unit 102, the air pole 114 of single battery 110 is by air pole side current collection
Body 134 is electrically connected with a connectors 150, and fuel electrodes 116 are by fuel electrodes side collector 144 and another 150 electricity of connectors
Connection.In addition, multiple power generation units 102 that fuel cell unit 100 is included are electrically connected in series.It therefore, can be from as defeated
1st protruding portion 14 of the 1st end plate 104 that terminal functions out and the 2nd protruding portion 16 of collector plate 18 take out single in each power generation
Electric energy generated in position 102.In addition, SOFC generates electricity at relatively high temperature (such as 700 DEG C~1000 DEG C), because
This, after activation, fuel cell unit 100 can also can be utilized by heater heating (not shown) and be generated by power generation
State of the heat to maintain high temperature until.
As shown in Figure 2 and Figure 4, the oxidant exhaust OOG ejected from the air chamber 166 of each power generation unit 102 is via oxygen
Oxidant gas is discharged intercommunicating pore 133 and is discharged to oxidant gas discharge manifold 162, is also discharged by way of setting to oxidant gas
The main part 28 of the gas passage component 27 of the position of manifold 162 and the hole of branch portion 29, have connect via with the branch portion 29
External discharge of the gas pipe (not shown) come to fuel cell unit 100.In addition, as shown in Figure 3 and Figure 5, it is single from each power generation
The exhaust combustion gases FOG that the fuel chambers 176 of position 102 eject is discharged via fuel gas discharge intercommunicating pore 143 to fuel gas
Manifold 172 is discharged, also 28 He of main part by way of the gas passage component 27 of setting to the position of fuel gas discharge manifold 172
The hole of branch portion 29, via the gas pipe ((not shown)) connected with the branch portion 29 to outside fuel cell unit 100
Portion's discharge.
A-3. the detailed construction of glass sealing material 52,54,56:
Fig. 6 is the explanatory diagram for indicating the structure of the 1st glass sealing material 52 of present embodiment.It has been shown in FIG. 6 the 1st
The SEM image (200 times) in the section XZ of glass sealing material 52.Hereinafter, by the above-mentioned orientation (up and down direction as Fig. 6
Z-direction) on size be known as " linear foot cun ", by the face direction orthogonal with the orientation (left and right directions as Fig. 6
X-direction) on size be known as " crossfoot cun ".
As shown in fig. 6, the 1st glass sealing material 52 contains multiple lengthwise crystal grain 200.Lengthwise crystal grain 200 is linear foot cun phase
Ratio (=linear foot cun/crossfoot cun, hereinafter referred to as " aspect rate ") for crossfoot cun is 1.5 or more the crystalline substance in needle-shaped extension
Grain.That is, lengthwise crystal grain 200 is the crystal grain extended along the direction intersected with following direction: being parallel to and the 1st glass sealing material
(X-direction, can be formed Y direction between two member of formation in the direction of the opposite face of two member of formation of 52 contacts
Gas leak path).In addition, two member of formation contacted with the 1st glass sealing material 52 are be fitted to bolt 22 upper
The nut 24 and the 1st end plate 104, the 2nd end plate 106 and gas passage member 27, gas passage component 27 of side and it is fitted to bolt
The nut 24 of 22 downside, these are equivalent to the 1st member of formation and the 2nd member of formation in claims.
As shown in fig. 6, including the lengthwise crystal grain that aspect rate is significantly more than 1.5 in multiple lengthwise crystal grain 200.Such as
This, the aspect rate of lengthwise crystal grain 200 more preferable 3 or more and 10 or less.In addition, for every in the 1st glass sealing material 52
In crystal grain contained by unit area, preferably 50% or more crystal grain is lengthwise crystal grain 200.In addition, at least one lengthwise crystal grain
200 linear foot cun is 30% or more size of the linear foot cun (thickness of orientation) of the 1st glass sealing material 52.Moreover,
The linear foot cun of more preferably at least 1 lengthwise crystal grain 200 is 50% or more size of the linear foot cun of the 1st glass sealing material 52.
In addition, the linear foot cun of the 1st glass sealing material 52 can determine as follows.It obtains upper comprising the 1st glass sealing material 52
The SEM image at end and both lower ends, based on the 1st glass sealing material 52 structure adjacent with the 1st glass sealing material 52
Difference, visuognosis of composition substance at component (the 1st member of formation, the 2nd member of formation) etc. are to the 1st glass sealing material 52
Top and bottom respective positions be determined, can according between the position of identified upper end and the position of lower end away from
From the linear foot cun for determining the 1st glass sealing material 52.
2nd glass sealing material 54 and the 3rd glass sealing material 56 also contain multiple lengthwise crystal grain 200 respectively.In addition, with
Two member of formation of the 2nd glass sealing material 54 contact are collector plate 18 and the 2nd end plate 106, with the 3rd glass sealing material 56
Two member of formation of contact are the connectors 150 and separator 120 of upside, these are equivalent to the 1st structure in claims
At component and the 2nd member of formation.In addition, glass sealing material 52,54,56 is equivalent to the glass capsulation portion in claims.
A-4. the manufacturing method of fuel cell unit 100:
Fig. 7 is the flow chart for indicating the manufacturing method of fuel cell unit 100 of above-mentioned structure.Firstly, on composition of preparation
The multiple member of formation (single battery 110, separator 120 etc.) (S110) for the fuel cell unit 100 stated.Then, above-mentioned
Position (the sealing pair that 1st glass sealing material 52, the 2nd glass sealing material 54 and the 3rd glass sealing material 56 should be formed
Between two components of elephant) glass material and kind layer (S120) before the crystallization of each glass sealing material 52,54,56 of configuration.
The position that each glass sealing material 52,54,56 should be formed refers to, in fuel cell unit 100 across each glass sealing material
52,54,56 and the space between the 1st adjacent member of formation and the 2nd member of formation.Specifically, the 1st glass sealing material 52
The position that should be formed refers to space, gas passage component 27 and the spiral shell between nut 24 and the 1st end plate 104 or the 2nd end plate 106
Space between female 24 or the 2nd end plate 106.In addition, the position that the 2nd glass sealing material 54 should be formed refers to the 2nd end plate 106
With the space between collector plate 18.In addition, the position that the 3rd glass sealing material 56 should be formed refers in each power generation unit 102
Across air pole side frame 130 and the space between adjacent separator 120 and connectors 150.
Kind layer (is also possible to this yuan by the substance containing element at least one kind of in Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce
The oxide of element) it is formed.Specifically, kind layer is by such as TiO2The coating that powder is formed.Kind layer is configured at glass capsulation material
Expect between at least one of the 52,54,56 and the 1st member of formation and the 2nd member of formation.Specifically, kind layer is formed in the 1st structure
At at least one opposite face in two opposite faces relative to each other between component and the 2nd member of formation.In addition it is also possible to
It is to prepare the glass material that the crystal seed containing the above-mentioned element contained by kind of layer can be precipitated in advance, by aftermentioned S140
Heat treatment, make crystal seed from glass material be precipitated, to form kind of a layer.Alternatively, it is also possible to be, in the preparation rank of member of formation
In section (S110), preparation is formed with the member of formation of kind of layer in opposite face in advance.
Then, each component for constituting fuel cell unit 100 is assembled, and fastens (S130) by bolt 22 and nut 24.At this point,
Make bolt 22 through the through hole 108 formed in each component.
Then, each component is assembled in S130 and the structural body that is formed is by the softening temperature (such as 700 with glass material
(DEG C)) heating, so that glass material melting is heated, to make glass material later with crystallized temperature (such as 850 (DEG C))
Material crystallization.In addition, at this point, the element contained by kind layer is functioned as crystal seed, thus glass sealing material 52,54,
56 form above-mentioned lengthwise crystal grain 200.By above process, the fuel cell unit 100 of above structure can be produced.
A-5. the effect of present embodiment:
Due to the fever that the power generation movement of fuel cell unit 100 (power generation unit 102) generates, fuel cell unit 100 is constituted
Each member of formation thermal expansion.For example, swollen across the adjacent separator 120 of the 3rd glass sealing material 56 and 150 heat of connectors
It is swollen.Due to the thermal expansion of separator 120, in the 3rd glass sealing material 56, in the lower surface side adjacent with separator 120
Point, it is applied with along the relative direction (above-mentioned orientation, hereinafter referred to as " longitudinal direction ") with separator 120 and connectors 150 just
The face direction (X/Y plane direction, hereinafter referred to as " transverse direction ") of friendship stretches the power of the lower face side part.In addition, due to connectors
150 thermal expansion, in the 3rd glass sealing material 56, in the upper surface side part adjacent with connectors 150, be applied with along
The power of the cross directional stretch upper surface side part.
Here, separator 120 and connectors 150 cause coefficient of thermal expansion different because of material difference, therefore, mutual heat is swollen
Bulk is different.Therefore, because the lower face side part of the 3rd glass sealing material 56 due to the thermal expansion of separator 120 by along
The upper surface side part of power stretching in the transverse direction and the 3rd glass sealing material 56 is due to the thermal expansion of connectors 150 by along transverse direction
Therefore the difference of the power of stretching generates lateral stress in the 3rd glass sealing material 56.If the stress of the transverse direction is in the 3rd glass
Sealing material 56 generates, then is easy to generate along the transverse crack being laterally extended in the 3rd glass sealing material 56.If generating transverse fissure
Line then forms the gas leak path that is connected to air chamber 166 with fuel chambers 176 in the 3rd glass sealing material 56, causes point
Leakproofness between spacing body 120 and connectors 150 is possible to impaired.
In contrast, according to the present embodiment, the 3rd glass sealing material 56 containing aspect rate be 1.5 or more it is multiple
Lengthwise crystal grain 200.Even if as a result, due to the lateral stress of the thermal expansion between separator 120 and connectors 150 the 3rd
Glass sealing material 56 generates, and due to lengthwise crystal grain 200, is easy to more preferential than transverse crack the 3rd along the longitudinal crack longitudinally extended
Glass sealing material 56 generates, and therefore, can make lateral stress release using longitudinal crack, is able to suppress separator 120 and mutually
Leakproofness between connected device 150 reduces.In addition, for the 1st glass sealing material 52 and the 2nd glass sealing material 54, similarly
Ground contains multiple lengthwise crystal grain 200, is able to suppress due to the thermal expansion difference across their two adjacent member of formation
Stress under the action of, cause the sealing between two member of formation to reduce.
In addition, the present invention is also possible to structure as following.
" a kind of electrochemical reaction battery pack, has:
Multiple single batteries, the single battery include electrolyte layer and across the electrolyte layer along the 1st direction that
This opposite air pole and fuel electrodes；
With one or more member of formation, which is characterized in that,
The electrochemical reaction battery pack has glass capsulation portion, glass capsulation portion and the multiple single battery and described 1
Two components contact in a or multiple member of formation, along the 1st direction opposite to each other, which contains glass
Glass,
Contain multiple crystal grain that the linear foot cun ratio very little relative to crossfoot is 1.5 or more, the linear foot in the glass capsulation portion
The very little size as on the 1st direction, the crossfoot cun is as the size on the 2nd direction orthogonal with the 1st direction."
In addition, the linear foot cun of at least one of multiple lengthwise crystal grain 200 contained by each glass sealing material 52,54,56 is
30% or more size of longitudinal thickness of each glass sealing material 52,54,56.Therefore, by making longitudinal crack compare transverse crack
It is easy to more preferably generate in each glass sealing material 52,54,56, so as to more effectively inhibit across each glass sealing material
52,54,56 and leakproofness between two adjacent member of formation reduces.Also, it is preferred that at least the 1 of multiple lengthwise crystal grain 200
A linear foot cun is 50% or more size of longitudinal thickness of each glass sealing material 52,54,56.Even if generating as a result,
Transverse crack, the progress of the transverse crack are also easy to be inhibited by lengthwise crystal grain 200, and as a result, it is possible to more effectively inhibit above-mentioned two
Leakproofness between a member of formation reduces.In addition, longitudinal thickness of each glass sealing material 52,54,56 with as each
The mutual separation distance in the part opposite along up and down direction of two components of sealed object is equal.
In addition, the manufacturing method of fuel cell unit 100 according to the present embodiment, across each glass sealing material 52,
54,56 and between two adjacent member of formation configuration contain at least one kind of member in Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce
The kind layer and glass material of element make glass material melting, crystallization, are formed well so as to efficiency and contain lengthwise crystal grain
200 each glass sealing material 52,54,56.
B. variation:
Technology disclosed in this description is not limited to above-mentioned embodiment, being capable of model without departing from its main purpose
Various forms are deformed into enclosing, can also for example be deformed as following.
In the above-described embodiment, as glass capsulation portion, instantiate be sandwiched in two member of formation relative to each other it
Between glass sealing material 52,54,56, but not limited to this, for example, it can be contacted with above-mentioned two member of formation,
The glass capsulation portion between two member of formation is not configured simultaneously.For example, being also possible in Fig. 4 to cover and will separate
The right side surface side at joint portion 124, the upper surface of separator 120, right side surface side and the list that part 120 and single battery 110 engage
The glass sealing material that the mode of the upper surface of body battery 110 configures.Alternatively, it is also possible to utilize alternative joints portion, glass capsulation portion
Separator 120 and single battery 110 are engaged and are closed by 124.Furthermore, it is also possible to separator 120 and single battery 110 it
Between configure both joint portion 124 and glass sealing material, separator 120 and single battery 110 are engaged and closing.In addition,
It is preferred that being configured with glass sealing material between single battery 110 and separator 120 part relative to each other.Above-mentioned
In the case of, separator 120 is equivalent to the member of formation in claims.In addition, glass sealing material is equivalent to claim
Glass capsulation portion in book.In addition, in this case, passing through the glass capsulation material in separator 120, single battery 110
Expect that contacted position is pre-formed with kind of a layer, above-mentioned lengthwise crystal grain 200 can be formed in glass sealing material.
In addition, at least one of glass sealing material 52,54,56 can also not contain lengthwise crystal grain 200.In addition, each glass
A part in sealing material 52,54,56 can also be formed by the material other than glass.In addition, in glass capsulation portion (glass
Glass sealing material 52,54,56 etc.) at least one section (such as XZ section of Fig. 6) parallel with up and down direction in, preferred glass
The ratio (the hereinafter referred to as the area ratio of lengthwise crystal grain 200) of the area of lengthwise crystal grain 200 in the predetermined area of glass sealing is
15% or more, more preferably 20% or more.In addition, the area ratio of lengthwise crystal grain 200 can pass through cutting for glass capsulation portion
The SEM image in face calculates the area of lengthwise crystal grain 200 contained in the predetermined area in glass capsulation portion to find out.
In addition, in the above-described embodiment, as two member of formation contacted with glass capsulation portion, being set as 24 He of nut
1st end plate 104 or the 2nd end plate 106, gas passage component 27 and nut 24 or the 2nd end plate 106, the 2nd end plate 106 and collector plate
18, separator 120 and connectors 150, but not limited to this.For example, fuel cell unit 100 be separator 120 and mutually
In the case where structure between connected device 150 or collector plate 18 configured with glass capsulation portion, separator 120 and connectors 150 or collection
Battery plate 18 is equivalent to two member of formation.
In addition, the linear foot of multiple lengthwise crystal grain 200 contained by each glass sealing material 52,54,56 cun be also possible to it is small
In 30% size of longitudinal thickness of each glass sealing material 52,54,56.
In the manufacturing method of fuel cell unit 100 shown in Fig. 7, in S120, kind of a layer can not also be configured.But,
By configuring kind of a layer, it can more reliably make the formation of lengthwise crystal grain 200.
In addition, in the above-described embodiment, the number for the power generation unit 102 that fuel cell unit 100 is included is essentially
One example, output voltage etc. required by the number fuel cell stack 100 for the unit 102 that generates electricity suitably are determined.
In addition, in the above-described embodiment, by the inner peripheral surface of the outer peripheral surface of the axle portion of each bolt 22 and each through hole 108 it
Between space be used as each manifold, replace, axial hole can also be formed in the axle portion of each bolt 22, by the hole be used as each discrimination
Pipe.Each through hole 108 alternatively, it is also possible to which each manifold to be inserted into each bolt 22 is provided independently from.
In addition, in the above-described embodiment, in the case where two power generation units 102 are adjacent to configuration, 1 connectors
150 are shared by two adjacent power generation units 102, even if being such situation, two power generation units 102 are also possible to distinguish
Have connectors 150.In addition, in the above-described embodiment, in fuel cell unit 100, power generation unit 102 on most
The connectors 150 of the downside of the connectors 150 of upside, power generation unit 102 under most are omitted, but these connectors 150
It can not also omit, but be provided with these connectors 150.
In addition, in the above-described embodiment, fuel electrodes side collector 144 is also possible to same with air pole side collector 134
The structure of sample, fuel electrodes side collector 144 and adjacent connectors 150 are also possible to integral member.It is empty alternatively, it is also possible to be
Air exhaustion side frame 130 is not insulator, and fuel electrodes side frame 140 is insulator.In addition, air pole side frame 130, fuel electrodes
Side frame 140 is also possible to multilayered structure.
In addition, the material of each component of formation in above embodiment is essentially to illustrate, each component can also be by other
Material is formed.
In addition, in the above-described embodiment, town gas is modified and is obtained the fuel gas FG of hydrogen-rich, but both may be used
Fuel gas FG is obtained with other raw materials from LP gas, lam-oil, methanol, gasoline etc., pure hydrogen can also be used as fuel gas FG.
In the present specification, across component (or certain part, following same of component) A and component B and component C are relative to each other
It is not limited to the component A form adjacent with component B or component C, including other constituent elements are between component A and component B or structure
Form between part C.Even also can for example, being provided with the structure of other layers between electrolyte layer 112 and air pole 114
It is relative to each other across electrolyte layer 112 to say into air pole 114 and fuel electrodes 116.
In addition, in the above-described embodiment, fuel cell unit 100 is that multiple plate shaped power generation units 102 are laminated
Structure, but the present invention can also be equally applicable to other structures, such as recorded in International Publication No. 2012/165409 that
The structure that the fuel cell of the multiple general cylindrical shapes of sample is connected in series.In this case, it is contacted with glass capsulation portion
Two member of formation be also possible to such as single battery and be formed with the hole of the partial insertion of the one end for single battery
Shell (manifold).In this case, glass capsulation portion is with the partial insertion with the formation in shell for the one end of single battery
The inner wall in hole and the mode of periphery face contact of single battery configure, shell is equivalent to the composition structure in claims
Part.
In addition, in the above-described embodiment, to utilize the oxygen contained by the hydrogen and oxidant gas contained by fuel gas
Between electrochemical reaction come the SOFC that generates electricity be object, but the present invention can also be equally applicable to it is anti-using the electrolysis of water
It answers and carries out the minimum unit i.e. electrolytic cell unit of the electrolytic cell (SOEC) of the soild oxide shape of the generation of hydrogen, has multiple electricity
Solve the electrolytic cell of pond unit.In addition, the structure of electrolytic cell is remembered such as such as Japanese Unexamined Patent Publication 2016-81813 bulletin
Carrying is well known like that, therefore, is not discussed in detail herein, in summary, is and the fuel cell unit in above-mentioned embodiment
100 same structures.That is, the fuel cell unit 100 in above-mentioned embodiment is renamed as electrolytic cell, will generate electricity unit
102 rename as electrolytic cell unit.But, when the operating of electrolytic cell, positive (anode) is become with air pole 114
And fuel electrodes 116 become the mode of cathode (cathode) to applying voltage two electrodes, also, supply conduct via through hole 108
The vapor of unstrpped gas.The cell reaction for causing water in each electrolytic cell unit as a result, generates hydrogen in fuel chambers 176,
Hydrogen is taken out to the external of electrolytic cell via through hole 108.In the electrolytic cell unit and electrolytic cell of such structure,
Also it is able to suppress in the same manner as above embodiment and is led under the action of the stress of the thermal expansion difference due to two member of formation
The leakproofness between two member of formation is caused to reduce.
Description of symbols
14, the 1st protruding portion；16, the 2nd protruding portion；18, collector plate；22, bolt；24, nut；27, gas passage component；
28, main part；29, branch portion；52,54,56, glass sealing material；57, insulating materials；100, fuel cell unit；102, it generates electricity
Unit；104,106, end plate；108, through hole；110, single battery；112, electrolyte layer；114, air pole；116, fuel electrodes；
120, separator；121, hole；124, joint portion；130, air pole side frame；131, hole；132, oxidant gas supply connection
Hole；133, intercommunicating pore is discharged in oxidant gas；134, air pole side collector；135, collector element；140, fuel electrodes side frame
Frame；141, hole；142, fuel gas supplies intercommunicating pore；143, intercommunicating pore is discharged in fuel gas；144, fuel electrodes side collector；
145, electrode counterpart；146, connectors counterpart；147, interconnecting piece；149, spacer；150, connectors；161, oxidant gas
Body imports manifold；162, manifold is discharged in oxidant gas；166, air chamber；171, fuel gas imports manifold；172, fuel gas
Manifold is discharged in body；176, fuel chambers；200, lengthwise crystal grain；FG, fuel gas；FOG, exhaust combustion gases；OG, oxidant gas；
OOG, oxidant exhaust.
Claims (11)
1. a kind of electrochemical reaction unit, has:
Single battery comprising electrolyte layer and across the electrolyte layer along the 1st direction air pole relative to each other and
Fuel electrodes；
With one or more member of formation,
The electrochemical reaction unit is characterized in that,
The electrochemical reaction unit has glass capsulation portion, the glass capsulation portion and the single battery and it is described one or more
Glass is contained in two components contact in member of formation, along the 1st direction opposite to each other, the glass capsulation portion,
Multiple crystal grain that the linear foot cun ratio very little relative to crossfoot is 1.5 or more are contained in the glass capsulation portion, and the linear foot cun is made
For the size on the 1st direction, the crossfoot cun is as the size on the 2nd direction orthogonal with the 1st direction.
2. electrochemical reaction unit according to claim 1, which is characterized in that
Described two components are that the single battery and at least part are opposite with the single battery on the 1st direction
The member of formation.
3. electrochemical reaction unit according to claim 2, which is characterized in that
The member of formation opposite with the single battery is separator, which is formed with through hole, is passed through described in encirclement
The part of through-hole is engaged with the peripheral part of the single battery, which marks off air chamber and face in face of the air pole
To the fuel chambers of the fuel electrodes.
4. electrochemical reaction unit according to claim 1, which is characterized in that
Described two components are 1st member of formation and 2nd member of formation relative to each other along the 1st direction.
5. electrochemical reaction unit according to claim 4, which is characterized in that
One of 1st member of formation and the 2nd member of formation are connectors.
6. electrochemical reaction unit according to any one of claims 1 to 5, which is characterized in that
The linear foot cun of at least one of the multiple crystal grain is the thickness in the 1st direction in the glass capsulation portion
30% or more.
7. electrochemical reaction unit described according to claim 1~any one of 6, which is characterized in that
The linear foot cun of at least one of the multiple crystal grain is the thickness in the 1st direction in the glass capsulation portion
50% or more.
8. a kind of electrochemical reaction battery pack has multiple electrochemical reaction units, which is characterized in that
At least one of multiple electrochemical reaction units is the electrochemical reaction according to any one of claims 1 to 7
Unit.
9. a kind of manufacturing method of electrochemical reaction unit, the electrochemical reaction unit have:
Single battery comprising electrolyte layer and across the electrolyte layer along the 1st direction air pole relative to each other and
Fuel electrodes；
One or more member of formation；And
It is in glass capsulation portion, with the single battery and one or more described member of formation, along the 1st direction that
Glass is contained in this opposite two components contact, the glass capsulation portion,
Multiple crystal grain that the linear foot cun ratio very little relative to crossfoot is 1.5 or more are contained in the glass capsulation portion, and the linear foot cun is made
For the size on the 1st direction, the crossfoot cun as the size on the 2nd direction orthogonal with the 1st direction,
The manufacturing method of the electrochemical reaction unit comprises the following steps:
The process for preparing the single battery and one or more member of formation；
The kind layer containing at least one kind of element in Ba, Ca, Mg, Al, La, Ti, Cr, Zr, Ce is configured between described two components
With the process of glass；And
In the state that described kind of layer and the configurations of glass are between described two components, make the glass melting, later
The glass crystallization after melting, thus the process for forming the glass capsulation portion.
10. the manufacturing method of electrochemical reaction unit according to claim 9, which is characterized in that
Described two components are that the single battery and at least part are opposite with the single battery on the 1st direction
Member of formation.
11. the manufacturing method of electrochemical reaction unit according to claim 9, which is characterized in that
Described two components are 1st member of formation and 2nd member of formation relative to each other along the 1st direction.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016226504 | 2016-11-22 | ||
| JP2016-226504 | 2016-11-22 | ||
| PCT/JP2017/041992 WO2018097174A1 (en) | 2016-11-22 | 2017-11-22 | Electro-chemical reaction unit, electro-chemical reaction cell stack, and electro-chemical reaction unit production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109964350A true CN109964350A (en) | 2019-07-02 |
| CN109964350B CN109964350B (en) | 2022-08-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780071821.6A Active CN109964350B (en) | 2016-11-22 | 2017-11-22 | Electrochemical reaction unit, electrochemical reaction battery, and method for producing electrochemical reaction unit |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US11394039B2 (en) |
| EP (1) | EP3547428A4 (en) |
| JP (1) | JP6511195B2 (en) |
| KR (1) | KR20190069532A (en) |
| CN (1) | CN109964350B (en) |
| WO (1) | WO2018097174A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6605164B1 (en) * | 2018-12-27 | 2019-11-13 | 日本碍子株式会社 | Fuel cell stack |
| FR3113443B1 (en) * | 2020-08-11 | 2022-09-23 | Commissariat Energie Atomique | Electrolysis or co-electrolysis reactor (SOEC) or fuel cell (SOFC) with stacking of electrochemical cells by pre-assembled modules, associated production method. |
| WO2023193879A1 (en) * | 2022-04-04 | 2023-10-12 | Ceres Intellectual Property Company Limited | Electrochemical cell assembly with insert |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3547428A1 (en) | 2019-10-02 |
| CN109964350B (en) | 2022-08-23 |
| US20200083545A1 (en) | 2020-03-12 |
| JP6511195B2 (en) | 2019-05-15 |
| KR20190069532A (en) | 2019-06-19 |
| JPWO2018097174A1 (en) | 2018-11-22 |
| US11394039B2 (en) | 2022-07-19 |
| EP3547428A4 (en) | 2020-07-22 |
| WO2018097174A1 (en) | 2018-05-31 |
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